Kinetics of nopyl acetate synthesis by homogeneously catalyzed esterification of acetic acid with nopol
DOI:
https://doi.org/10.17533/udea.redin.n89a03Keywords:
activity coefficients, nopol, reaction rate, equilibrium constant, sulfuric acidAbstract
The esterification of nopol with acetic acid to produce nopyl acetate using sulfuric acid as homogeneous catalyst was studied. The reactions were carried out in a batch reactor, at different temperatures (50, 60, 70 and 80 °C), catalyst concentrations (0.0184, 0.0275, 0.0367 and 0.0480 molL−1 and molar ratio of acetic acid to nopol (1: 1, 1:2, 1:3 and 1: 4); the chemical equilibrium composition was measured at those reaction conditions. It was found that the equilibrium composition is a weak function of temperature, equilibrium conversion was 63, 68, 71 and 75% at 50, 60, 70 and 80°C, respectively. The reaction was described with a simple power-law model with a second-order kinetic model for both the forward and the backward reaction, using concentration and activities which were predicted by the Universal Functional group Contribution (UNIFAC) method for considering non-ideal behavior of the liquid phase. The forward reaction rate and the equilibrium constants increased with temperature; the relation of the pre-exponential factor with the catalyst amount was evaluated. The activation energy and pre-exponential factor estimated for the forward reaction using the kinetic model based on concentration, were respectively, 28.08 kJmol−1 and 11126 Lmol−1h −1 with a concentration of catalyst of 0.0275 M. Using the kinetic model based on activities, the forward reaction rate constant was 28.56 kJmol−1 and the kfo,act was 33860 Lmol−1h −1 . The enthalpy (34.90 kJmol−1 ) and the entropy (0.12 kJmol−1K−1 ) of reaction were determined using van’t Hoff equation.
Downloads
References
E. Akbay and M. Altıokka, “Kinetics of esterification of acetic acid with n-amyl alcohol in the presence of amberlyst-36,” Appl. Catal. A: Gen., vol. 396, no. 1-2, pp. 14–19, Apr. 2011.
S. H. Ali, A. Tarakmah, S. Merchant, and T. Al-Sahhaf, “Synthesis of esters: Development of the rate expression for the dowex 50 Wx8-400 catalyzed esterification of propionic acid with 1-propanol,” Chem. Eng. Sci., vol. 62, no. 12, pp. 3197–3217, Jun. 2007.
H. Pardel, S. Sarron, and C. Roy, “α-terpineol from Hydration of Crude Sulfate Turpentine Oil,” J. Agric. Food Chem., vol. 49, no. 9, pp. 4337–4341, Aug. 2001.
T. Chatterjee and D. Bhattacharyya, “Synthesis of terpene esters by an immobilized lipase in a solvent-free system,” Biotechnol. Lett., vol. 20, no. 9, pp. 865–868, Sep. 1998.
P. A. Mullen, “Fragrance-containing insect repellant compositions,” U.S. Patent 2 005 002 980, Jan. 6, 2005.
D. Belsito and et al, “A toxicologic and dermatologic assessment of cyclic and non-cyclic terpene alcohols when used as fragrance ingredients,” Food Chem. Toxicol., vol. 46, no. 11, pp. S1–S71, Nov. 2008.
K. B. D. Garbe and H. Surburg, Common Fragrance and Flavor Materials: Preparation, Properties and Uses, 4th ed. Weinheim, Germany: Wiley-VCH, 2001.
W. Poucher, Poucher’s Perfumes, Cosmetics and Soaps — Volume 1: The Raw Materials of Perfumery, 1st ed. Netherlands: Springer, 1991.
A. Corma and M. Renz, “Water-resistant lewis-acid sites: carbonyl-ene reactions catalyzed by tin-containing, hydrophobic molecular sieves,” Arkivoc, vol. 8, pp. 40–48, 2007.
D. Opdyke, Monographs on Fragrance Raw Materials: A Collection of Monographs Originally Appearing in Food and Cosmetics Toxicology, 1st ed. New York, USA: Pergamon Press Inc, 1979.
P. E. JagadeeshBabu, K. Sandesh, and M. B. Saidutta, “Kinetics of Esterification of Acetic Acid with Methanol in the Presence of Ion Exchange Resin Catalysts,” Ind. Eng. Chem. Res., vol. 50, no. 12, pp. 7155–7160, Apr. 2009.
J. Lilja and et al, “Kinetics of esterification of propanoic acid with methanol over a fibrous polymer-supported sulphonic acid catalyst,” Applied Catalysis A: General, vol. 228, no. 1–2, pp. 253–267, Mar. 2002.
R. Rönnback and et al, “Development of a kinetic model for the esterification of acetic acid with methanol in the presence of a homogeneous acid catalyst,” Chem. Eng. Sci., vol. 52, no. 19, pp. 3369–3381, Oct. 1997.
Y. Liu, E. Lotero, and J. G. Goodwin, “A comparison of the esterification of acetic acid with methanol using heterogeneous versus homogeneous acid catalysis,” J. Catal., vol. 242, no. 2, pp. 278–286, Sep. 2006.
S. Geyer, W. Zeiger, and R. Mayer, “Säurekatalysierte Umwandlungen in der Monoterpenreihe,” Z. Chem., vol. 6, no. 4, pp. 138–146, Apr. 1996.
M. Chiplunkar, M. Hong, M. F. Malone, and M. F. Doherty, “Experimental study of feasibility in Kinetically-Controlled Reactive Distillation,” A´IChE J, vol. 51, no. 2, pp. 464–479, Feb. 2005.
C. Beula and P. T. Sai, “Kinetics of Esterification of Acetic Acid and Ethanol with a Homogeneous Acid Catalyst,” Ind. Chem. Eng., vol. 57, no. 2, pp. 177–196, 2015.
G. Jyoti, A. Keshav, J. Anandkumar, and S. Bhoi, “Homogeneous and Heterogeneous Catalyzed Esterification of Acrylic Acid with Ethanol: Reaction Kinetics and Modeling,” Int. J. Chem. Kinet., vol. 50, no. 5, pp. 370–380, Mar. 2018.
G. Jyoti, A. Keshav, and J. Anandkumar, “Experimental and Kinetic Study of Esterification of Acrylic Acid with Ethanol Using Homogeneous Catalyst,” Int. J. Chem. Reactor Eng., vol. 14, no. 2, pp. 571–578, 2016.
S. W. Liu and et al, “Reactions of α-pinene using acidic ionic liquids as catalysts,” J. Mol. Catal. A: Chem, vol. 279, no. 2, pp. 177–181, Jan. 2008.
S. Liu, C. X. Xie, S. T. Yu, F. S. Liu, and K. H. Ji, “Esterification of α-pinene and acetic acid using acidic ionic liquids as catalysts,” Catal. Commun., vol. 9, no. 7, pp. 1634–1638, Apr. 2008.
L. Li and et al, “Synthesis of terpinyl acetate using octadecylamine ethoxylate ionic liquids as catalysts,” Res. Chem. Intermed., vol. 39, no. 5, pp. 2095–2105, May. 2013.
D. J. Tao and et al, “Tuning the acidity of sulfonic functionalized ionic liquids for highly efficient and selective synthesis of terpene esters,” J. Ind. Eng. Chem., vol. 41, pp. 122–129, Sep. 2016.
X. Chen and T. O. Z. Xu, “Liquid phase esterification of acrylic acid with 1-butanol catalyzed by solid acid catalysts,” Appl Catal A: Gen, vol. 180, no. 1-2, pp. 261–269, Apr. 1999.
J. Lilja and et al, “Esterification of different acids over heterogeneous and homogeneous catalysts and correlation with the taft equation,” J Mol Catal A: Chem., vol. 182–183, pp. 555–563, May. 2002.
Y. Liu, E. Lotero, and J. G. Goodwin, “Effect of water on sulfuric acid catalyzed esterification,” J Mol Catal A: Chem., vol. 245, no. 1-2, pp. 132–140, Feb. 2006.
E. Lotero and et al, “Synthesis of Biodiesel via Acid Catalysis,” Ind. Eng. Chem. Res., vol. 44, no. 14, pp. 5353–5363, Jan. 2005.
M. Mekala and V. R. Goli, “Kinetics of esterification of methanol and acetic acid with mineral homogeneous acid catalyst,” Chin. J. Chem. Eng., vol. 23, no. 1, pp. 100–105, Jan. 2015.
Z. Xu and K. Chuang, “Kinetics of acetic acid esterification over ion exchange catalysts,” Can. J. Chem. Eng., vol. 74, pp. 493–500, Mar. 1996.
M. de Jong, R. Feijt, E. Zondervan, T. Nijhuis, and A. de Haan, “Reaction kinetics of the esterification of myristic acid with isopropanol and n-propanol using p-toluene sulphonic acid as catalyst,” Appl Catal A: Gen., vol. 365, no. 1, pp. 141–147, Aug. 2009.
T. Pöpken, L. Götze, and J. Gmehling, “Reaction Kinetics and Chemical Equilibrium of Homogeneously and Heterogeneously Catalyzed Acetic Acid Esterification with Methanol and Methyl Acetate Hydrolysis,” Ind. Eng. Chem. Res., vol. 39, no. 7, pp. 2601– 2611, Jun. 2000.
D. J. Tao and et al, “Kinetics for the Esterification Reaction of n-Butanol with Acetic Acid Catalyzed by Noncorrosive Brønsted Acidic Ionic Liquids,” Ind. Eng. Chem. Res., vol. 50, no. 4, pp. 1989–1996, Jan. 2011.
O. Levenspiel, Chemical Reaction Engineering, 3rd ed. New York, USA: John Wiley Sons, 1999.
D. Othmer and S. Rao, “n-Butyl Oleate from n-Butyl Alcohol and Oleic Acid,” Ind. Eng. Chem., vol. 42, no. 9, pp. 1912–1919, Sep. 1950.
M. Altiokka and A. Citak, “Kinetics study of esterification of acetic acid with isobutanol in the presence of amberlite catalyst,” Appl. Catal. A: Gen., vol. 239, no. 1-2, pp. 141–148, Jan. 2003.
G. D. Yadav and P. H. Mehta, “Heterogeneous Catalysis in Esterification Reactions: Preparation of Phenethyl Acetate and Cyclohexyl Acetate by Using a Variety of Solid Acidic Catalysts,” Ind. Eng. Chem. Res., vol. 33, no. 9, pp. 2198–2208, Sep. 1994.
R. Aafaqi, A. R. Mohamed, and S. Bhatia, “Kinetics of esterification of palmitic acid with isopropanol using ptoluene sulfonic acid and zinc ethanoate supported over silica gel as catalysts,” J Chem Technol Biotechnol, vol. 79, pp. 1127–1134, Sep. 2004.
T. Komón, P. Niewiadomski, P. Oracz, and M. E. Jamróz, “Esterification of acrylic acid with 2-ethylhexan-1-ol: Thermodynamic and kinetic study,” Applied Catalysis A: General, vol. 451, pp. 127–136, Jan. 2013.
S. Chandane, A. Rathod, K. Wasewar, and S. Sonawane, “Process optimization and kinetic modeling for esterification of propionic acid with benzyl alcohol on ion-exchange resin catalyst,” Korean J Chem Eng., vol. 34, no. 4, pp. 987–996, Apr. 2017.
A. Kouzekonani and M. Mahdavian, “Modeling of esterification in a batch reactor coupled with pervaporation for production of ethyl acetate catalyzed by ion- exchange resins,” Adv. Environ. Technol, vol. 2, pp. 69–75, 2015.
A. Fredenslund, R. Jones, and J. Prausnitz, “Group Contribution Estimation of Activity Coefficients in Nonideal Liquid Mixtures,” AIChE J., vol. 21, no. 6, pp. 1086–1099, Nov. 1975.
B. E. Polling, J. M. Prausnitz, and J. P. O’Connell, The properties of gases and liquids, 5th ed. NY, USA: McGraw-Hill, 2001.
B. Erdem and M. Cebe, “Kinetics of esterification of propionic acid with n-amyl alcohol in the presence of cation exchange resins,” Korean J. Chem. Eng., vol. 23, no. 6, pp. 896–901, Nov. 2006.
L. Ma, Y. Han, K. Sun, J. Lu, and J. Ding, “Kinetic and thermodynamic studies of the esterification of acidified oil catalyzed by sulfonated cation exchange resin,” J. Energy Chem., vol. 24, no. 4, pp. 456–462, Jul. 2015.
S. Schwarzer and U. Hoffmann, “Experimental Reaction Equilibrium and Kinetics of the Liquid phase Butyl Acrylate Synthesis Applied to Reactive Distillation Simulations,” Chem. Eng. Technol., vol. 25, no. 10, pp. 975–980, Oct. 2002.
J. E. House, Principles of chemical kinetics, 2nd ed. New York, USA: Elsevier Inc., 1997.
Downloads
Published
How to Cite
Issue
Section
License
Copyright (c) 2018 Revista Facultad de Ingeniería Universidad de Antioquia
This work is licensed under a Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International License.
Revista Facultad de Ingeniería, Universidad de Antioquia is licensed under the Creative Commons Attribution BY-NC-SA 4.0 license. https://creativecommons.org/licenses/by-nc-sa/4.0/deed.en
You are free to:
Share — copy and redistribute the material in any medium or format
Adapt — remix, transform, and build upon the material
Under the following terms:
Attribution — You must give appropriate credit, provide a link to the license, and indicate if changes were made. You may do so in any reasonable manner, but not in any way that suggests the licensor endorses you or your use.
NonCommercial — You may not use the material for commercial purposes.
ShareAlike — If you remix, transform, or build upon the material, you must distribute your contributions under the same license as the original.
The material published in the journal can be distributed, copied and exhibited by third parties if the respective credits are given to the journal. No commercial benefit can be obtained and derivative works must be under the same license terms as the original work.
Twitter